Diphenolic acid, epoxide compositions



atent Ofihce 2,90%30 Patented Oct. 6, 1959 DIPHENOLIC ACID, EPOXIDECOMPOSITIONS Sylvan Owen Greenlee, West Lafayette, Ind., assignor to S.C. Johnson & Son, Inc., Racine, Wis.

No Drawing. Application September "19, *1958 Serial No. 761,923

10 Claims. (Cl. 260-19) THE INVENTION AND OBJECTS IN GENERAL Theinvention relates to new compositions resulting from the reaction ofpolyepoxides and diphenol carboxylic acids and/or said compositionsmodified with aldehyde condensates in regulated proportions to givevaluable materials useful in the manufacture of moldings, adhesives,films, etc. The epoxides used in making the new compositions contain anaverage of more than one epoxide group per molecule and are free fromfunctional groups or other than epoxide, carboxyl, and hydroxyl groups.The diphenol carboxylic acids are acids having an aliphatic-aromaticstructure and containing hydroxyl groups in addition to the carboxylgroup. The aldehyde condensate modifiers are fusible materials havingfree reactive sites. The invention includes the initial reactionmixtures as well as the intermediate and final reaction products derivedtherefrom.

An object of this invention is the production of new compositions fromepoxides and diphenol carboxylic acids and said compositions modifiedwith aldehyde condensates to form resins, varnishes, moldingcompositions, adhesives, etc.

Another object of this invention is the production of intermediatereaction products from the initial reaction mixtures of epoxides anddiphenol carboxylic acids and said compositions modified with aldehydecondensates which are capable of further reaction on the application ofheat to form insoluble, infusible products.

Another object of this invention is the production of new admixtures ofthe materials set-forth hereinabove which are stable at ordinarytemperatures for relatively long periods of time, yet which may bepolymerized into insoluble, infusible products with or without theaddition of catalysts by the application of heat.

These and other objects and advantages will appear from the followingmore detailed description, with par ticular reference to specificexamples which are to be considered as illustrative only.

In general the polyepoxides contemplated for use herein are compoundscontaining an average of more than one and up to about 20 epoxide groupsper molecule. Epoxide groups for the purpose of this specification referto groups wherein the epoxy oxygen bridges adjacent carbon atoms. Suchcompositions, free from functional groups other than epoxide, carboxyland hydroxyl groups, are reactive with active hydrogen containing groupsincluding the phenolic and carboxyl groups supplied by the contemplateddiphenol carboxylic acids.

Typical epoxides which have been found to be operable are complexresinous polyepoxides, resinous polyepoxide polyesters, epoxidizednatural oils and aliphatic polyepoxides.

The diphenol carboxylic acids contemplated for use herein are the 4,4bis(hydroxyaryl) pentanoic acids and their equivalent, exemplified by4,4 bis(4--hydroxyphenyl) pentanoic acid. The aldehyde condensates areprepared from low molecular weight aldehydes and ammonia derivativescapable of being condensed with an aldehyde or from low molecular weightaldehydes and phenols capable of being condensed with an aldehyde. It isnecessary that the condensate remain soluble and fusible as well ascontain reactive methanol groups or an active hydrogen atom attached tosome other function group.

The compositions of the instant invention are prepared by reacting anepoxide with a diphenol carboxylic acid and if desired modifying saidcomposition with the before-mentioned aldehyde condensates usually inthe presence of heat. Having generally described and set forth theobjects of the invention, a more detailed description of operablecomponents and reaction conditions will be given.

OPERABLE DIPHENOL CARBOXYLIC ACIDS The diphenol carboxylic acidscontemplated for use herein must have two hydroxyaryl groups attached toa single carbon atom. The preparation of such an aryloxy acid is mostconveniently carried out by condensing a keto acid with the desiredphenol. To the best of applicants knowledge, any keto acid or ester isoperable in which a keto group is connected to a carboxy or carboalkoxyradical through an alkylene radical of at least 2 cabon atoms; however,experience in the preparation of bisphenol and related compoundsindicates that the carbonyl group of the keto acid should be positionednext to a terminal methyl group in order to obtain satisfactory yields.Further, while a broad class of acids is contemplated such as the ketosubstituted pentanoic, hexanoic and heptanoic acids, the pentanoic acid,levulinic acid, is preferred since it is readily available.

Prior copending applications, Serial Nos. 464,607 and 489,300 filedOctober 25, 1954, and February 18, 1955, respectively, disclose a numberof illustrative compounds suitable for use as the diphenol carboxylicacid and methods of preparing the same. These materials which arereferred to for convenience as diphenol carboxylic acids or by the tradename DPA, consist of the condensation products of levulinic acid andphenol, substituted phenols or mixtures thereof. It is to be understoodthat the phenolic nuclei of the diphenol carboxylic acids may bestubstituted witht any group whichwill not interfere with the reactionscontemplated herein. Such groups are the halo, nitro and alkyl groups of1 to 5 carbon atoms. The chloro and bromo phenols are the preferredhalogenated materials: although it is possible under proper conditionsto condense fluoro substituted phenols with a keto acid. Diphenolcarboxylic acids derived from substituted phenols such as the alkylatedphenols are sometimes more desirable than the products obtained fromunsubstituted phenols due to properties impartred by the substitutedgroups. For

instance, the alkyl groups provide better solvent solubility in selectedsolvents, flexibility and water resistance. However, the unsubstitutedproduct is usually more readily purified. In the before mentionedcondensation reac tion between the phenol and keto acid it has beenfound, as one would expect, that the reaction occurs so that thephenolic hydroxyl group of the diphenol carboxylic acid is in a positionpara or ortho to the point of attachment of the hydroxyaryl radical tothe pentanoic acid. Very little or no condensation occurs at the metaposition.

Examples 1 to 4 inclusive, illustrate the preparation of "typical-diphenol carboxylic acids. However, it should be understood that theinvention is not intended to be limited thereby. Proportions expressedare parts by weightunless otherwise indicated. Acid values as usedherein represent the number of milligrams of KOH required to neutralizea one gram sample.

- Examplel A mixture consisting of 376 parts of phenol, 116 parts 'oflevulinic acid, and 250 parts of 37% aqueous hydrohot water gave a whitecrystalline compound melting at 171172 C. with an acid value of 196.

Softening points .as used herein were run by Durrans Mercury Method(Journal of Oil and Colour Chemists Association, 12, 173-5, 1929).

ExampleZ 240.5 grams (2.18 mols) ortho cresol, 156 grams (37%) HCl, and145 grams levulinic acid were charged to a 2-liter round bottom flaskequipped with thermometer, reflux condenser and mechanical agitator. Thetemperature Was raised to 50 C. in approximately 1 hour and held in thisrange for an additional 72 hours. The recovered material was washed 6times with boiling water before steam distilling. The resultant crudematerial had an acid value of 156, a saponification No. of 206 and wasrecovered at 74% of theoretical based on levulinic acid.

This crude material was refluxed with aqueous sodium hydroxide forapproximately 1 hour and the material re-acidified, washed and filtered.The material was recrystallized from hot benzene and dried in a vacuumoven. The resultant material had an acid value of 169, theoretical 178,saponification value of 175, theoretical 178 and a'melting point of149-l50 C.

Example 3 363parts of the ethyl esterof 4,4-bis(4-hydroxypheny1)pentanoicacid prepared as in Example 1 and 344 parts of sulfonylchloride were charged to a 3 necked flask equipped with thermometer,reflux condenser, and mechanical stirrer. The reaction immediatelyexothermed and was cooled with a water bath maintaining the temperatureat approximately 25 C. for 1 hour. The reaction charge became thick andthen solidified with a pronounced temperature rise. The reaction mixturehad a yellow color. Excess 'su'lfonyl chloride was removed underslight'pressure. Theobtained ester had a chlorine content of 21.38%corresponding to the addition of approximately2 chlorine atoms(theoretical equals 18.5%). Thechlorinated ester was saponified toobtain the cor responding acid.

Example 4 172 parts DPA'prepared as in Example 1 and 450 parts glacialacetic acid were charged to a 3 necked flask equipped with athermometer, reflux condenser, and mechanical stirrer. The resultantsolution was tan in: color. 264 parts of benzene were added to thecharge: before cooling to 0 C. in an ice bath. At this tem-- perature,drop-wise addition of 85.8 parts 70% nitric acid diluted with 66 partsof glacial acetic acid was begunc The complete addition required 3 hoursand 45 minutes with the reaction temperature never exceeding 0 C. Thereaction charge at the end of the addition was a clear dark reddishsolution. The charge was allowed to stir at temperatures between 5 and20 C. for approximately 12 hours. At the end of this time, a heavyorange precipitate had formed. The precipitate was filtered and washed 3times with distilled water before it was vacuum dried. Theresultantcrude material recovered at 84.5 of theoretical, had an acidvalue of 488 (theoretical=447) and a melting point of 1024 C. The crudematerial was recrystallized from a mixture of hot ethanol and water togive a fine yellow crystalline material having a melting point of137.5-" C., a nitrogen content of 7.20% (theoretical equal 7.44%.) andan acid value of 445.

Additional operable diphenol carboxylic acids include acids containingchloro, bromo, nitro and alkyl groups of 1 to '5 carbon atomsexemplified by '4,4-bis('4-'hydroxy-3-ethyl phenyl)-pentanoic acid, 4,4-bis(4 -hydroxy- 3,5-isopropyl phenyD-pentanoic acid, 4,4-bis(4-hydro,xy-Z-ethyl phenyl)- pentanoic acid, 4,4-bis(2-hydroxy-4-butylphenyl-hpentanoic acid, 4,4-bis(4 hydroxy-2,5-diarnyl phenyl) pentanoicacid, 4,4-bis(4-hydroxy-3-nitro phenyl)- pentanoic acid,4,4-bis(2hydroxy3nitro-phenyl):pentanoic acid,4,4-bis(4-hydroxy-3-methylphenyl) pentanoic acid, 4,4-bis(4-hydroxy-3-amyl phenyD-pentanoic acid,4,4-bis(4-hydroxy-3-chloro phenyD-pentanoic acid, 4 (4-hydroxyphenyl)4-(4-hydroxy-3-amy1 phenyD-pentanoie acid,4-.(4-hydroxyphenyl)-4-(2-hydroxy4-chlorophenyl) pentanoic acid,4-(4-hydroxyphenyl)-4-(4-hydroxy-3, S-dibromo phenyl)-pentanoic acid,4-(4.-hydroxyphenyl)- 4-(2-hydroxy-4-nitro phenyl)-pentanoic acid,4-(4-hydroxyphenyl) 4 (4-hydroxy-3-sulfo phenyl)-pentanoic acid,4-(4-hydroxypl1enyl) 4 -.(2-hydroxy-3,5-dimethyl phenyl) -pentanoicacid, 4,4-bis(2-hydroxy-4-butyl phen- .yl)-pentanoic acid,4,4-bis(2-hydroxy-5 methyl-3 chloro phenyl) pentanoic acid,4,4:bis(4-hydroxy3,5-dibromo phenyl)-pentanoic acid,4,4-bis(4-hydroxy-3,5-dinitro phenyl)-pentanoic acid,4,4-bis(2-hydroxy-3 nitro-S methyl phenyl) pentanoic acid,4,4-bis(4-hydroxy-3- methyl-5 chloro phenyl)-pentanoic acid, 5,5-bis(4hydroxy phenyl)-hexanoic acid, 5,5-bis(4-hydroxy-3-methylphenyl)-hexanoic acid, 5,5-bis(4-hydroxy-3-nitro phenyl) hexanoic acid,and 5,5-bis(4-hydroxy-3-chloro phenyl)- hexanoic acid.

OPERABLE EPOXIDES Illustrative of the epoxide compositions which may beemployed in this invention are the complex epoxide resins which arepolyether derivatives of polyhydric phenols with such polyfunctionalcoupling agents as polyhalohydrins, polyepoxides, or epihalohydrins.These compositions may be described as polymericpolyhydric alcoholshaving alternating aliphatic chains and nuclei connected to each otherby ether linkages, containing terminal epoxide groups and free fromfunctional groups It should be This would be illustrated by I toIIIbelowwhere n equals zero. Preparation of these epoxide materials as-wellas illustrative examples are described in U.S. Patents 2,456,408,2,503,- 726, 2,615,007, 2,615,008, 2,668,807, 2,688,805 .and 2,698,315.Well-known commercial examples. ofthese resins are the Eponresinsmarketed by the Shell ChemicalCorporation. Illustrative of thepreparation of these epoxide resins are the following reactions whereinthe difunctional coupling agent is used in varying molar excessiveamounts:

portioning reactants in the polyester formation and regulating theepoxidation reaction, polyepoxides having up Polyhydrie phenol and anepihalohydrin bis(hydroxyphenyl)isopropylidene excess epichlorohydrinIEI CHOHLO OOHzCHOHOHr -O OCHflCHOHg aqueous ---e alkali Og OH; 72 C H;CE; I

Polyhydrie phenol and a polyepoxido bis(hydroxyphenyl)isopropylideneexcess butylene dioxide ({H2CHOHOHOHQLO 0CH2CHOHCH0HCH2LO OCH2CHOHC/HCH2heat CH3 CH, 7L CH3 \OH3 II Polyhyclrie phenol and a polyhalohydrinbis(hydroxyphenyl)isopropylidene excess alpha-glycerol diehlorohydrinCHZOHCHQLO 0CHgOHOHCH -O OCHZGHCH aqueous alkali CH CH n CH CH; III

As used in the above formulas, 11 indicates the degree of polymerizationdepending on the molar ratio of reactants. As can be seen from theseformulas, the complex epoxide resins used in this invention containterminal epoxide groups and alcoholic hydroxyl groups attached to thealiphatic portions of the resin, the latter being formed by thesplitting of epoxide groups in the reaction of the same with phenolichydroxyl groups. Ultimately, the reaction with the phenolic hydroxylgroups of the polyhydric phenols is generally accomplished by means ofepoxide groups formed from halohydrins by the loss of hydrogen andhalogen as shown by the following equation:

Other epoxide compositions which may be used include the polyepoxidepolyesters which may be prepared by esterifying tetrahydrophthalicanhydride with a glycol and epoxidizing the product of theesterification reaction. In the preparation of the polyesters,tetrahydrophthalic acid may also be used as well as the simple esters oftetrahydrophthalic acid such as dimethyl and diethyl esters. There is atendency with tertiary glycols for dehydration to occur under theconditions used for esterification so that generally the primary andsecondary glycols are the most satisfactory in the polyester formation.Glycols which may be used in the preparation of this polyestercomposition comprise, in general, those glycols having 2 hydroxyl groupsattached to separate carbon atoms and free from functional groups whichwould interfere with the esterification or epoxidation reactions. Theseglycols include such glycols as ethylene glycol, diethylene glycol,triethylene glycol, tetrainethylene glycol, propylene glycol,polyethylene glycol, neopentyl glycol, and hexamethylene glycol.Polyepoxide polyesters may be prepared from these polyesters byepoxidizing the unsaturated portions of the tetrahydrophthalic acidresidues in the polyester composition. By properly proto 12 or moreepoxide groups per molecule may be readily prepared. These polyepoxidepolyester compositions as well as their preparation aremore fullydescribed in a copending application having Serial No. 503,323, filedApril 22, 1955, now abandoned.

Polyepoxide compositions useful in this invention also include theepoxidized unsaturated natural oil acid esters, including theunsaturated vegetable, animal, and fish oil acid esters made by reactingthese materials with various oxidizing agents. These unsaturated oilacid esters are long chain aliphatic acid esters containing from about15 to 22 carbon atoms. These acids may be esterified by simplemonohydric alcohols such as methyl, ethyl, or decyl alcohol, bypolyhydric alcohols such as glycerol, pentaerythritol, polyallylalcohol, or resinous polyhydric alcohols. Also suitable are the mixedesters of polycarboxylic acids and long chain unsaturated natural oilacids with polyhydric alcohols, such as glycerol and pentaerythritol.These epoxidized oil acid esters may contain more than 1 up to 20epoxide groups per molecule. The method of epoxidizing these unsaturatedoil acid esters consists of treating them with various oxidizing agents,such as the organic peroxides and the peroxy acids, or with one of thevarious forms of hydrogen peroxide. A typical procedure practiced in theart consists of using hydrogen peroxide in the presence of an organicacid, such as acetic acid and a catalytic material, such as sulfuricacid. More recently epoxidation methods have consisted of replacing themineral acid catalyst with a sulfonated cation exchange material, suchas the sulfonated copolymer of styrene divinylbenzene.

The epoxide compositions which may be used in preparing the compositionsof this invention also include aliphatic polyepoxides which may beillustrated by the products obtained by polymerizing ally'l glycidylether through its unsaturated portion. In the polymerization of theseethers there is probably some polymerization occurring through theepoxide groups, and in addition Other aliphatic polyepoxides usefulin.this invention may be illustrated by the poly(epoxyalkyl) ethersderived from polyhydric alcohols. in general, be prepared by reacting analiphatic polyhydric alcohol with an epihalohydrin in the presence of asuitable catalyst and in turn dehydrohalogenating the product to producethe epoxide composition. The production of these epoxides may beillustrated by the reaction of glycerol with epichlorohydrin in thepresence of boron trifluoride followed by dehydrohalogenation withsodium aluminate as follows:

BFa CHOH 3 ornoHoHzcn a CHOH O CHzOCHzCHOHCHzCl CHZOC'HZCHCHZ O NaAlOgCHOGHzCHOHCHgOl CHOCHzICHCHz 0 CHQOOHQOHOHOH2C1 CHZOCH CHOH It is to beunderstood that such reactions do not give pure compounds and that thehalohydrins formed and the epoxides derived therefrom are of somewhatvaried character depending upon the particular reactants, theirproportions, reaction time and temperature. In addition to epoxidegroups, the epoxide compositions may be characterized by the presence ofhydroxyl groups and halogens. Dehydrohalogenation afiects only thosehydroxyl groups and halogens which are attached to adjacent carbonatoms. Some halogens may not be removed in this step inthe event thatthe proximate carbinol group has been destroyed by reaction with anepoxide group. These halogens are relatively unreactive and are not tobe considered as functional groups in the conversion of the reactionmixture of this invention. The preparation of a large number of thesemixed polyepoxides is described in the Zech patents, US. 2,538,072,2,581,- 464, and 2,712,000. Still other polyepoxides which have beenfound to be valuable are such epoxide compositions as diepoxy butane,diglycid ether, andepoxidized polybutadiene.

Immediately following will be a description or illustration ofpreparations of polyepoxides which will be used in examples .ofcompositions of this invention.

The complex resinous ,polyepoxides used in the examples and illustrativeof the commercially prepared products of this type are the Epon resinsmarketed by Shell Chemical Corporation. The following table gives theproperties of some Epon resins which are prepared by the condensation inthe presence of alkali of bis(4-hydroxyphenyl) isopropylidene'with amolar excess of epichlorohydrin in varying amounts.

1 Based on 40% nonvolatile inbutyl Carbitol at 25 0.

Examples 5 through 7 describe the preparation of typical polyepoxidepolyesters.

Example 5 PREPARATION OF POLYESTER FROM TETRAHYDRO- PI-ITHALIC ANHYDRIDEAND E'IHYLENE GLYCOL Ina v3-necked flask provided with a thermometer,mechanical agitator, and a reflux condenser attached These materialsmay, 1

. tent.

through a water trap was placed a mixture of 3 mols oftetrahydrophthalic anhydride and 2 mols of n-butanol. After melting thetetrahydrophthalic anhydride in he presence of the butanol, 2 mols ofethylene glycol were added. Thereaction mixture was gradually heatedwith agitation to 225' C. at which point a suflicient amount of xylenewas added to give refluxing at esterification temperature. The reactionmixture was then heated with continuous agitation at 225-235 C. until anacid value of 4.2 was obtained. This product gave an iodine value of128.

EPOXIDATION O THE POLYESTER RESIN Ina 3-necked flask provided with athermometer, a mechanical agitator, and a reflux condenser was placed107 parts of the dehydrated acid form of a cation exchange resin (Dowex50 X-8, 5.0- mesh, Dow Chemical Company, a sulfonatedstyrenedivinylbenzene copolymer containing about 8% divinylbenzene, thepercent divinylbenzene serving to control the amount of crosslinkage.The Dowex resins are discussed in publications entitled Ion ExchangeResins No. 1 and Ion Exchange Resins No. 2, copyright 1954 by DowChemical Company, the publications having form number Sp32-254 and S 3l354, respectively) and 30 parts glacial acetic acid. The mixture ofcation exchange resin and acetic acid was allowed to stand until theresin had completely taken up. the acid. To this mixture was added 200parts of the polyester resin dissolved in an equal weight of xylene. Tothe continuously agitated reaction mixture was added dropwise over aperiod of 45 minutesto 1 hour, 75 parts of 50% hydrogen peroxide. Thereaction temperature Was held at 60 C. requiring the application of someexternal heat. (In some preparations involving other polyesterresins,sufi'icient exothermic heat is produced during the addition of hydrogenperoxide so that no external heat isurequired, or even some externalcooling may be required.) The reaction was continued at 60 C. until amilliliter sample of the reaction mixture analyzed less than 1milliliter of 0.1 N sodium thiosulfate in an iodometric determinationofhydrogen peroxide. The product was then filtered, finally pressing thecation exchange resin filter cake. The acid value of the total resinsolution was 42. The percent non-volatile of this solution amounting to400 parts was :50. This 400 parts of solution was thoroughly mixed with110 parts of the dehydrated basic form of Dowex 1 (an anion exchangeresin of the quaternary ammonium type. Dowex 1 is astyrenedivinylbenzene copolymer illustrated by the formula RR' N+OH-where R represents the styrenedivinylbenzene matrix and R' is a methylgroup, manufactured by the Dow Chemical Company). The resulting mixturewas then filtered followed by pressing as much of the solution aspossible from the anion exchange resin cake. This product had an acidvalue of 4.5 and an epoxide equivalent of 288 based on a nonvolatileresin content of 42.0%. The epoxide values as discussed herein weredetermined by refluxing for 30 minutes a 2-gram sample with 50milliliters of pyridine hydrochloride in excess pyridine. (The pyridinehydrochloride solution was prepared by adding 20 milliliters ofconcentrated HCl to a liter of pyridine.) After cooling to roomtemperature, the sample is then back-titrated with standard alcoholicsodium hydroxide.

Example 6 Following the procedure of Example 5, a polyester resin wasprepared from 5 mols of tetrahydrophthalic anhydride, 4 mols ofdiethylene glycol, and 2 mols of n butanol. This product had an acidvalue of 5.3 and an iodine value of 107. This polyester resin wasepoxidized in the manner previously described to give an epoxideequivalent weightof 371 ou the nonvolatile con The nonvolatilecontent.of this resin solution as prepared was 40.2%. 7'

Example 7 Example 8 Admex 710, an epoxidized soyabean oil having anequivalent weight to an epoxide of 263, was dissolved in methyl ethylketone to a nonvolatile content of 50%. Admex 710, a product of theArcher-Daniels-Midland Company, has an acid value of 1, a viscosity of3.3 strokes at 25 C. and an average molecular weight of 937.

Examples 9 and 10 describe the preparation of aliphatic polyepoxides.

Example 9 In a reaction vessel provided with a mechanical stirrer andexternal cooling means was placed 276 parts of glycerol and 828 parts ofepichlorohydrin. To this reaction mixture was added 1 part of 45% borontrifluo ride ether solution diluted with 9 parts of ether. The reactionmixture was agitated continuously. The temperature rose to 50 C. over aperiod of 1 hour and 45 minutes at which time external cooling with icewater was applied. The temperature was held between 50 and 75 C. for 1hour and 20 minutes. To 370 parts of this product in a reaction vesselprovided with a mechanical agitator and a reflux condenser was added 900parts of dioxane and 300 parts of powdered sodium aluminate. Withcontinuous agitation this reaction mixture was gradually heated to 92 C.over a period of 1 hour and 50 minutes, and held at this temperature for8 hours and 50 minutes. After cooling to room temperature, the inorganicmaterial was removed by filtration. The dioxane and low boiling productswere removed by heating the filtrate to 205 C. at 20 mm. pres- Sure togive a pale yellow product. The epoxide equivalent of this product wasdetermined by treating a 1- gram sample with an excess of pyridinecontaining pyridine hydrochloride (made by adding'20 cc. of concentratedhydrochloric acid per liter of pyridine) at the boiling point for 20minutes and back-titrating the excess pyridine hydrochloride with 0.1Nsodium hydroxide using phenolphthalein as indicator and considering oneHCl as equivalent to one epoxide group. The epoxide equivalent on thisproduct was found to be 152.

Example 10 In a 3-necked flask provided with a thermometer, a mechanicalagitator, a reflux condenser and a dropping funnel was placed 402 partsof allyl glycidyl ether. With continuous agitation the temperature wasraised to 160 C. at which time one part of a solution of methyl ethylketone peroxide, dissolved in diethyl phthalate to a 60% content, wasadded. The temperature was held at 160 165 C. for a period of 8 hours,adding one part of the methyl ethyl ketone peroxide solution eachminutes during this 8-hour period. After the reaction mixture had stoodovernight, the volatile ingredients were removed by vacuum distillation.The distillation was started at 19 mm. pressure and a pot temperature of26 C. and volatile material finally removed at a pressure of 3 mm. and apot temperature of 50 C. The residual product had a molecular weight of418, and equivalent weight to epoxide content of 198, the yieldamounting to 250 parts.

The nonvoli6 OPERABLE ALDEHYDE CONDENSATE Two general classes ofaldehyde condensates are com templ'ated for preparing the modifiedproducts of this invention, those prepared from ammonia derivatives andthose derived from phenols, with the choice being dependent on the enduses and characteristics desired. For instance, if the end use were tobe a white enamel, the ammonia derivative-aldehyde condensates wouldprobably be chosen because of their extremely light initial color andtheir good color retention. The phenols are somewhat darker in color andhave a tendency to yellow upon aging. For the most desirable non-polarsolvent solubility, the phenol-aldehyde condensates would be the properchoice since the ammonia derivative-a1- dehyde condensates usuallyrequire some butanol and xylol present to give the desirable solubility.For certain applications, the butanol odor is objectionable and at timesbutanol is incompatible with other resins which are used. Adhesion tometals also appears to be better in the phenol-aldehyde condensates.From an economic standpoint, the phenol-aldehyde condensates areadvantageous, being lower in price.

The aldehyde-ammonia derivatives condensation prodnets are formed by thereaction of aldehydes with amines or amides such as urea, thiourea, andtheir derivatives, melamines and sulfonamides. It is necessary that theammonia derivative contain at least one NH group. Thus nitriles andtertiary amines which are also considered ammonia derivatives areexcluded. Otherwise the definition reads on amides and primary andsecondary amines. It is well known that such materials including anumber of their derivatives react with formaldehyde to formaldehyde-amine or aldehyde-amide condensates. Exemplary derivatives aresubstituted urea, thio urea, or melamine such as the long-chainalkyl-substituted materials which impart oil or organic solventsolubility. Suitable sulfonamides include aromatic mononuclearsulfonamides such as toluene sulfonamide, polynuclear sulfonamides suchas naphthalene sulfonamide, sulfonamides of aromatic po'lynuclear ethersand monoor polyfunctional sulfonamides. In addition to melamine, otheroperable ammonia derivatives containing the azide bridge are the aminodiand triazines.

In the condensation of aldehydes with the organic ammonia derivatives,initially the reaction appears to be the addition of aldehyde to theorganic ammonia derivative to form primarily intermediate alkylolcompounds. These compounds will further condense to form more resinousmaterials, combining with each other through alkylene bridges formedbetween the nitrogen atoms of the compounds.

In the alkylol condensate and in the more condensed products of anadvanced stage of condensation, there are hydrogen atoms present in thehydroxyl groups which have been formed in the production of the alkylolcondensate and which have not been destroyed by further condensation.There are also an appreciable number of hydrogen atoms attached tonitrogen atoms of the amide or amine groups present in the condensationproducts. These hydrogens contained in the hydroxyl groups and the amideor amine groups are active with respect to epoxide groups and will reacttherewith in the reaction mixtures of this invention to form complex,crosslinked products.

In general, the condensation products of ammonia derivatives andaldehydes contemplated herein are partial and intermediate reaction orcondensation products of aldehydes, particularly formaldehyde, withamines or amides, or mixtures thereof. The reactions which produce suchcondensation products involve the removal of amino or amido hydrogenatoms from the ammonia derivative. Therefore, it should be understoodthat an ammonia derivative as stated hereinbefore, .in order to besuitable for condensation with an aldehyde, must contain.

be used with the .epoxides and the diphenol car hox-ylic acids to :formthe new -.cornp;ositions and reactioriprodnets of this invention. Thus.the condensates may be made "by various processes known in the .art do;the manufacture or aldehyde-ammonia=dcfiivative resins, me- :sulting inwater-soluble, iallcohol soluble or aoil seluble types,

, Fer usflfherein, the aldehyde-ammonia derivative c'ondensate may e inits monomeric form which is essent ally an al kylol .or polyalkylolproduct or it may be highly condensed. It issuitable as long as=it isistillqfusible and is-soluble-in .or compatible with the epoxideroomposition and the diphenol carboxylic acid composition with which-itis to be reacted.

Many .of'the commercial products derived from the-reaction of urea,thiou-rea, or melamine with formaldehyde are mixedpr-oducts made byreacting'the formaldehyde with mixtures of these materials. Suchcomposite or mixed reaction products can advantageously be used forreaction with the epoxides'and the diphenol car iboxylic acids accordingto the present invention. In addition, many of the present daycommercial resins derived from aldehydes and urea, thiourea, ormelamine, or a mixture thereof, are prepared in the presence .ofalcoholic or other solvents which take part in the reaction and becomean integral part of the resulting resin composition. This is illustratedby theproducts prepared in the presence of butyl alcohol in which casethe butyl alcohol to some extent condenses with the alkylolgroups of thealdehyde condensate to give hutyl'etherresiducs as a part of thefinalcomposition. Such modified products are also suitable. In some cases itmay be desirableto use an ammonia derivative-aldehyde condensate whichis completely soluble in a common solvent or a mixture of solvents usedto dissolve the epoxide and the diphenol carboxylic acid. Solutionsprepared in this manner can'be applied as a coating and'the solventsubsequently evaporated before the main reaction betweenthe epoxide,diphenol carboxylic acid and condensate takes place,

Examples 11 to 15, inclusive, describe the preparation of typicalammonia derivative-aldehyde condensatessuitable for use herein.

Example 11 In a 3-liter 3-neck flask providedwith a mechanical agitator,a thermometer, and reflux condenser was placed 120 parts of urea, 600parts of 37% aqueous formaldehyde, and 1040 parts of n-butyl alcohol.With-continuous agitation the reaction mixture was heated to refluxtemperature and the refluxing continued for a period of 1 hour. At thispoint a water trap was placed between the reflux condenser and flask andfilled with toluene. Distillation was continued until 315 parts of waterwere removed from the reaction mixture. The resulting mixture was cooledto room temperature,filtered, and 1030 parts of a clear, water-whitesyrupy liquid isolated.

Example 12 The procedure of preparation including the removal of waterwas the same as that used in Example 11. A'mixture of 120 parts of urea,148 parts of thiourea, '950-parts of 37% aqueous formaldehyde, and 800parts of-n-butyl alcohol was used to give a final yield of 1175 parts ofa clear, almost colorless, syrupy liquid.

Example 14 'In'a 3 -liter Sheckflask'protrided with a mechanicalcondenser and filled with toluene.

i=2 agitator, a thermometer, and a. reflux condenser was placed 378parts of melamine, 840 parts-of 37% aqueous formaldehyde, and 725 partsof n-butyl alcohol. With continuous agitation the reaction mixture washeated to reflux temperature and the refluxing continued for aperiod of30 minutes. At this point a-water trap'wasplaoed in the distillin'gcolumn between the flask and the reflux The refluxing was continueduntil a total of 590 parts of water had been removed from. the reactionmixture. The product amounting to 1342 parts was a clear,water-whiteflheavy; syrupy liquid.

Example 15 Ina 3-liter 3-nec-k flask provided with a mec hanicalagitator, a thermometer, and a reflux condenser was placed 1370 parts ofp-toluenesulfonamide and 640 parts of 37% aqueous'form'aldehyde the pHof whichhad been previously adjusted to 6.0 with potassium acidp'hthalate and sodium hydroxide. With continuous agitationthe re actionmixture was heated to reflux temperature over-a period of 40 minutes andthe refluxing continued for a period of 15 minutes. At this point thereaction-mixture was allowed to cool and the water decanted from theresin. The resin was washed- 3 times with warm water and finallydehydrated in vacuum at 30-50 mmfpre'ssure, using a maximum flasktemperature of "C. "to yield 1245 par-ts ofwater-white resinous solid.

In examples 11 to 15 inclusive, the ammonia derivative can be replacedby other materials'which have a NH group with the free valences beingfilled by hydrogen or carbon atoms. Thistherefore includes amides and"primary and secondary amines such as the ureas, thioureas, melamines,sulfonamides, and alkyl-substituted derivatives thereof. It is onlynecessary that the material "be capable of condensing with an aldehyde.

The second class of condensates suitable for modifying the compositionsherein described are those which contain reactive phenolic hydroxylgroups formed by the reaction of phenols and aldehydes. Phenol andformalde- .hyde react to form a variety of reaction products dependingupon the proportions and conditions of reaction. These include productssuch as phenol alcohols having bothphenolic and alcoholic hydroxylgroups, and products of the diphenol-methane type containing phenolichydroxyl groups only. The condensation of phenol and formaldehyde can becarried out with theme of acidor alkaline condensing agents and in somecasesby first combining the aldehyde with an alkali such as ammoniatoform hexarnethylenetetrarnine and'reacting the latter with the phenol.The phenol-aldehyde resins at an initial or intermediate stage ofreaction are intended to be included in'the term phenol-aldehydecondensates asusedherein.

In general, the phenol-aldehyde condensates should not have theircondensation carried so far as to become insoluble and nonreactive. Itis preferred in the preparation of the instant compositions that they beused at an intermediate stage or at a stage of reaction such "that theycontain reactive phenolic hydroxyl groups orb'oth phenolic and alcoholichydroxyl groups. This is'desirable in order to permit a proper blendingofthe phenolaldehyde condensate with the polyepoxides and diphenolcarboxylic acid for subsequent reaction therewith.

The phenol-aldehyde condensates may-he derived from mononuclear phenols,polynuclear phenols, monohydric phenols, or polyhydric phenols. Thecritical requirement for'the condensate is that it be compatible'withthepolyepoxides and diphenol carboxylic acids or withthe two reactants in asolvent used as a reaction medium. The phenol-aldehyde condensate whichis essentially a polymethylol phenol rather than a polymer maybe used inthe preparation of the new phenol-aldehyde, polyepoxide, diphenolcarboxylic acid products,'orit 'mayhe used after further condensation,in which case s'oine of the methylol groups are usuallyconsidered-tolhave'disample 18 a simple phenol.

appeared in the process of condensation. Various socalled phenolicresins which result from the reaction of phenols and aldehydes, andparticularly from common phenols or cresols and formaldehyde, areavailable as commercial products both of an initial and intermediatecharacter. Such products include res-ins which are readily soluble incommon solvents or readily fusible so that they can be admixed with theepoxides and diphenol carboxylic acid and reacted therewith to form theproducts of this invention.

In selecting a phenol-aldehyde condensate one may choose either theheat-converting or the permanently fusible type. For example, theformaldehyde reaction products of such phenols as carbolic acid,resorcinal, and 2,2-bis(4-hydroxyphenyl)propane readily convert toinfusible, insoluble compositions on the application of heat. On theother hand, some of the para alkylated phenols, as illustrated by ptert-butylph'enol, produce permanently fusible resins on reaction withformaldehyde. Even though fusible condensates are employed, however,insoluble, infusible products result when they are heated in combinationwith the epoxides and the diphenol carboxylic acid described.

Examples 16 to 18, inclusive, describe the preparation of some of theoperable phenol-aldehyde condensates which may be used in combinationwtih the polyepoxides and diphenol carboxylic acids to form the productsherein described. It is to be noted that the three examples are drawnfrom distinct classes of phenols and are meant to be representative ofthe broad class of phenols. Thus, in Example 16, the phenol is adihydroxy dinuclear phenol, in Example 17 an alkyl-substituted phenol,and in Ex- The examples, therefore, illustrate the unsubstitutedmonohydric phenols, the substituted monohydric phenols, and thepolynuclear phenols.

Example 16 In a 3-liter 3-neck flask provided with a mechanicalagitator, a thermometer, and a reflux condenser was placed 912 parts ofBisphenol A, 960 parts of 37% aqueous formaldehyde, and 2.3 parts ofoxalic acid. With continuous agitation, the reaction mixture was heatedto the reflux temperature and refluxing continued for a period of 1hour. mixture to cool to around 50 C. the water layer was removed bydecantation. The phenol-formaldehyde layer was then washed three timeswith water which in each case was removed by decantation. The lastportion of water was removed by distillation at reduced pressure using awater aspirator system which gave pressure around 30-40 mm. Thetemperature during the removal of this last portion of water ranged from7 -90 C. The product, amounting to 1065 parts, was a clear, heavy,syrupy material.

Example 17 The procedure of preparation, including the dehydration step,was the same as that used in Example 16. A mixture of 1000 parts ofp-tert-butylphenol, 1067 parts of 37% aqueous formaldehyde, and parts ofsodium hydroxide was used to give a final yield of 1470 parts 0 a clear,almost colorless syrupy product.

Example 18 Again a reaction procedure including the dehydration step,was the same as that used in Example 16. A mix- After permitting thereaction placed by other phenols including ottho, meta, and para GENERALREACTION CONDITIONS AND CHAR- ACTERISTICS OF THE NEW COMPOSITIONS Inmaking the new compositions, the polyepoxide and diphenol carboxylicacid or such compositions modified with aldehyde condensates areadmixed. in suitable proportions and reaction will proceed merely by theapplication of heat. More specifically the reaction is etiected byheating the mixtures at elevated temperatures, usually in the range ofabout 75-250 C. Catalysts are unnecessary, but in certain cases it maybe desirable to speed up the reaction by the use of catalysts, such asboron trifluoride adducts, sodium phenoxides, and mineral acid typecatalysts.

The reaction mixtures and final reaction products of this invention maybe prepared by using varying ratios of epoxide to diphenol carboxylicacid. The quantities of reactants employed in a given instance willdepend upon the characteristics desired in the final product. Flexibleconversion products can be obtained from the proper selection ofepoxide, diphenol carboxylic acid, and phenolaldehyde condensate. Ingeneral, operable products are those in which the ratio of epoxide todiphenol carboxylic acid on an equivalent weight basis ranges from about6:1 to 1:6 with the preferred range, because of the general over-allcharacteristics, being from 2:1 to 1:2. In instances where an aldehydecondensate is used as a modifier, operable amounts on a weight basis ofthe combined epoxide and diphenol carboxylic acid range up to about 90%,but from a practical standpoint, the preferred percentage is about 10%to 35%.

Compositions containing the polyepoxides and the diphenol carboxylicacids or such compositions modified with aldehyde condensates may beused as mixtures or at varying intermediate stages of reaction. Theinitial mixtures or intermediate reaction products which are soluble incommon organic solvents may be blended in solution in proper proportionsand the solutions then applied as an impregnant for fabrics or paper, orfor the formation of protective coating films. Subsequent heatingfunctions to remove thesolvent and bring about polymerization to theinsoluble, infusible state. For other uses, the initial or intermediatemixture may be used without a solvent, giving directly a compositionwhich, on the application of heat, converts to an infusible, insolublefinal product.

In making the new compositions and products herein described, thepolyepoxides and the diphenol carboxylic acid or such compositionsmodified with aldehyde condensates may be used in regulated proportionswithout the addition of other materials. For certain uses, othercomponents are often advantageously added, including filling andcompounding materials, plasticizers, pigments, etc. Compositions whichtend to give somewhat brittle products on conversion to the insoluble,infusible state are advantageously compounded with plasticizers. Formost applications, it is possible to obtain suitable flexibility andtoughness by regulating the proportions and types of reactingingredients, thereby obviating the need for plasticizers.

The application of heat'to the mixtures herein set forth may involveseveral chemical reactions. It will be appreciated that the reactionsinvolved are .very complex and the extent to which each takes place willvary with the temperature used in heat treating, the period of timetherefor, and with the particular types of polyepoxides, aldehydecondensate, if used, and diphenol carboxylic acid chosen. While it isnot desired to be limited by any theoretical explanation of the exactnature of these reactions, it seems probable that conversion to thefinal polymericproducts is accompanied by direct: polymerization of theepoxide groups inter 'se; reaction of the epoxide groups with methylolhydroxyl groups; reaction of the epoxide groups with phenolic hydroxylgroups, and reaction of epoxide groups with active hydrogen attached toa nitrogen atom, all of which take place to some extent simultaneouslyin forming the final products.

The present invention provides a wide range of reaction compositions andproducts including initial mixtures of the polyepoxides, aldehydecondensates, and the diphenol carboxylic acids, partial or intermediatereaction products of such mixtures and compositions containing suchintermediate reaction products as well as final reaction products. Ingeneral, the initial mixtures, as well as the intermediate reactionproducts unless too highly polymerized, are soluble in solvents of thelacquer type, such as ketone or ester solvents.

'In addition to having outstanding physical properties, such ashardness, toughness, and flexibility, the final infusible, insolubleproducts have outstanding chemical properties, such as high resistanceto oxidation, water, alkali, acids and organic solvents. It has alsobeen observed that the final conversion products possess un-. usuallygood adhesion to most surfaces including metal, glass, wood, andplastics. This property of outstanding adhesion to a wide variety ofsurfaces gives the subject products high potential value for use informulating adhesives. This property is also of extreme value informulating protective coating films for use on many types of surfaces.The adhesion characteristics are probably due to the fact that even inthe converted, infusible state, the compositions contain a relativelyhigh percentageof highly polar groups, such as ether groups, estergroups, and alcoholic and phenolic hydroxyl groups. Despite the highpercentage of polar groups in the insoluble, in-

fusible products of this invention the tolerance for water 35 isunusually low, apparently due :to the high molecular 16 weight and rigidcross-linked structure of the final com positions.

EXPERIMENTAL 0 7 Examples 19 to 156, inclusive, illustrate thepreparation of insoluble, infusible protective coating films from thecompositions of this invention. In the preparation of the compositionfor heat curing to .form the protective coating films, each ofthediphenol carboxylic acids, and the polyepoxides with the exception ofepoxidized polyesters were dissolved in methyl ethyl ketone to anonvolatile content of '60%.. The epoxidi-zed polyesters were -used .atthe nonvolatile and in the solvent in which they were prepared. Thealdehyde condensates were dissolved in 'a mixture of methyl ethyl ketoneand 15 butanol to a nonvolatile content of 40-60%. Mixtures of thediphenol vcarboxylic acids and polyepoxides or such compositionsmodified Wit-l1 aldehyde condensates were found to .be stable forextended periods .of time-at normal temperatures. Mixtures of thesolutions were spread on panels with a .002 Bird applicator and thefilms were baked for periods of .30 to 90 minutes .at temperaturesranging from ISO-200 C. Proportions as used in the following .tablerefer to .parts by weight and are .based on the nonvolatile content ofthe solutions of reactants.-

, In a number of examples setout inthe following table catalysts .areemployed to accelerate the reaction. lIn-the table the catalyst used .isdesignated by .a letter .corresponding .to the following key:

Catalyst; Conversion Filmzresistance Alde- Exaniple hyde Diphe- .HoursN0. Polyepoxide Parts conden- Parts nolie Parts H20 at 5% sate acidT-ype Parts Time Temp. (100 0.) aqueous rs) 0.) NaOH (at 25 O.)

19 Epon 864..-. 76.2 0 1. 0.5 175 35+ 76+ 20.-- do 76. 2 D 10. 4 .5 17535+ 76+ 21... 2.0 C .14 .5 175. .12 22... 14.3 C .14 5 i 175. ..25 5523..- 7.2 E 5 185 12+ 76+ 24... 7. 2 'C O9 5 185 35+ 76+ 25. 7.2 D '1. 2.5 175 35+ 76+ 26. 4.6 .D 1.2 .5 175 22+ 27 7. 2 O 14 5 175 35+ 76+ 27.2 -D 1.1 .5 185 '5357-l- 76+ 29. 14.3' D 1.0 .5 175 .33. 7 25 30. 23120 =1. 82 5 185 21 76+ 31 23. 2 D 2. 52 5 175 (35 76+ 32. 5. 7 O 03 5 175.25 '33... 9. 5 C .91 .5 175 7. 5 76+ 34... 9. 5 D 1. 26 5 185 17 2835--- 49 O .02 .5 175 55 t 32 36... 72 5 185 .3 .33 '37.-. 72 .5 175 .2.33 38... 40 5 185. 4 2 39.. 19.1 1. 25; 185 8 5 40. 19.1 D 3.08 .5 1753 .8 41 1911 O .68 .5 1 175 2 l 42. 19. 1 D 1. 54 5 175 6. '43. 19. 1D 1. 54 5 185 '6. 75 44. 19. 1 G 34 5 6. 75 45... 19. 1 O .34 5 7. 0046... 72 A 3.8 .5 200, 5.5 .47... 72 A 5.7 5 185 -3.5 4S... 143 A 5.3 5200 .25 49... 40 r A 5.73 .5 200 3 50... 72 'A "5.5 .5 200 '17 51... '72A :8.3 .5 185 18.5 52... 214 A 5. 5 5 200 12 '53. 20 .4 -11 5 200 '6 54.95. 5 A 5. 8 5 200 13 5 95. 5 A 8. 7 5 185 13 56. 20 'A 6.3 .5 185 5 5.57. Ex. 7. Ex. 1 :57 A 5.8 .5 .200 -3 t 58. Epon 1001... .0 Ex. 2.-.. lA 3 .5 200 33 59... Epon 562.... .5 Ex.2- 1.5 -A .2 5 200 75 '50-.- Epon1004--. 1.0 Ex. 4.--- .5 B .05 1. 0 206 1 20 61... Epon 1001... 2.0 Ex.3 .5 A .2 .5 200 3 100+ "62-.. Epon 1004... 1.0 1 0 1.0 B .07 5 200 2863 -Epon1061--. 1.0 Ex. 16... 1 0 -Ex.=4..-. .5- B .05 .5 200 .75 21Catalyst Conversion Film resistance Aldex mple hyde Diphe- Hours ypoxide Parts conden- Parts 110115 Parts H O at 5% sate acid Type PartsTime Temp. (100 0.) aqueous (hrs.) 0.) N 5011 (at 25 C.)

64 Epon 562.... 2,0 Ex. 17... 1.0 1.0 B .07 .5 200 33 .33 po .5 Ex.17... 1. 0 1. 0 B .08 .5 200 1 .88 66.. Epon 562---- Ex. 11.-. 5 l. 5 B.05 .5 200 3 1 57- Epon 1001.-. 5 Ex. .25 1. 0 B .08 1. 0 200 5 pon09 1. 0 Ex. 12... 1. 0 1. 0 B .05 .5 200 .5 1. 5 59- Epon 1001.-. 1. 0Ex. 11... 1. 0 1. 5 B .07 .5 200 5 .2 70. 11 15111004.-. .25 Ex. 11-...75 1.0 B .08 1.0 200 .75 .25 p n 562- .5 Ex. 15... 2. 0 1. 0 B .05 .5200 10 1 1 0 186 280 Ex. 11-.. 280 75 o 1.44 .5 185 20 90 73. Epon1001.-. Ex. 11... 125 47.5 0 .5 .5 185 20 90 74 pon 004. 250 Ex. 11-.-125 18.2 0 .5 .5 185 20 90 75 E9011 1007..- 9. 5 0 18 5 185 20 76 p1009.-. 3. 0 14 5 185 20 90 po 864..- 33. 8 0 1. 29 .5 185 20 90 p 0047. 5 0 .5 .5 185 0. 83 90 79. Epon 1004..- 13. 2 0 .5 .5 185 0. 88 9080. Epon 1007..- 9. 5 o 18 5 185 7. 5 90 Pon 1009..- 9. 5 0 18 .5 185 0.17 90 82.. -....d0 9.5 0 15.0 .5 175 4.5 15 pon 854.--. 75. 0 O 1. 44 5185 20 90 90 10 23.8 0 .9 .5 185 20 90 pon 1004.-- 28. 5 O 55 .5 185 2090 E9911 1 7. 8. 4 0 .25 5 185 20 90 pon 1009.-. 8. 9 0 .15 .5 185 20 9088.. Epon 854..-. 33.8 0 1. 29 5 185 20 90 p n 12. 0 0 .9 .5 185 20 90 155 100 28. 5 0 55 5 185 20 90 1.. Epon 100 5. 7 O .25 5 185 20 90 pon100 9. 5 0 18 5 185 20 90 98.. Epon 854 75. 0 0 1. 52 5 185 7 ED01110047.5 G .6 .5 185 5 140 ED011100 27 28.5 0 .55 .5 185 0.17 140 95.. Epon1007-.- 9. 5 0 18 .5 185 0. 88 140 p 0 9- 9. 5 O .18 .5 185 0. 08 23 9872, 0 5 200 2. 5 38 40 A 4.8 .5 200 5.5 8 40 A 8.8 .5 200 2.5 38 72 A8.8 .5 200 1.0 4.5 72 A 5. 8 5 200 15+ 0. 25 20 A 6.3 .5 185 2.5 3.5 72A 4.8 .5 200 7.0 .4 20 A 8.0 .5 200 .8 .5 20 A 8.0 .5 200 1.5 20 A 10. 05 200 15+ 0. 25 57 A 4.0 .5 200 2+ 2.5 57 A 4.2 .5 200 5+ 2.5 72 A 2.5.5 200 2 4.5 57 A 8. 8 5 200 15+ 0. 25 40 A 5. 8 1. 0 200 15+ 0. 25 95 01.8 .5 185 27 0.57 95 0 1.8 .5 185 15 2.5 47. 5 0 1. 8 5 185 27 8.75 95O 1.8 .5 185 27 0.75 28.75 0 1. 8 5 185 27 89 95 O 1.8 .5 185 27 0.1228.75 0 1. 8 5 185 27 7. 5 190 0 1. 8 .5 185 27 1. 75

95 0 1.8 .5 185 27 .13 4. 75 0 18 5 11+ 114+ 47. 5 O .5 5 185 11+ 114+125. Epon 1004.-- 28. 5 O .55 .5 185 2. 5 1 127... .-d0 2.4 0 .09 .5 1851.5+ 114+ 128-.- Epon 1007.-. 95 O .18 .5 185 1.25 40 129-.- --d0 95 o.18 .5 185 .83 114+ Epon 1001..- 47.5 0 .5 .5 185 15+ 140+ 183..- --do2.4 0 .18 .5 185 5+ 114+ 184..-

Epon 1004.-. 28.5 0 .55 .5 185 15+ 140+ 185..- Epon 1007.-. 9. 5 0 .18.5 185 15+ 140+ 136... do .63 0 .04 .5 185 1.5+ 114+ 187-.- Epon 1009...9. 5 O 18 5 185 15+ 140+ 188... .do 3 9.5 O .18 .5 175 5+ 114+ 139-.- 1510111004... 28.5 0 .55 .5 185 3 114+ 140..- Epon 1009... .84 0 .04 .5175 1 114+ 141..- 192.5 72 A 5.8 .5 200 5+ 5.5 142.-- 72 A 5.8 .5 200 51 5 148..- 72 0 5. 3 .5 200 9. 5+ 7+ 144. 42 O 5. 3 .5 200 5. 5+ 10+145. 72 0 11 5 200 9. 5+ 0. 75 145. 20 0 8 5 200 14. 5+ 5. 5+ 147. 72 A5. 8 .5 200 0. 17 2. 5 148. 20 0 2 5 200 14. 5+ 14. 5+

Example 157 262 parts Example 8, 95 parts 4,4b1s(4-hydr0xypheny1) Areactlon mixture was prepared by admixmg 50 pentanolc and, and 15.8parts boron trlfluonde trlethparts of the phenol-aldehyde condensate ofExample 17, 75 anolamine complex. The aldehyde condensate and Adaeomeomex 710 were used as 50% nonvolatile methyl ethyl ketone solutions andthe acid was used as a 50% nonvolatile dioxane solution. The mixture wasspread on glass panels in Wet fihns of .002" thickness, and cured byheating at 200 C. for 30 minutes. were hard, tack-free, and flexible,and they withstood aqueous sodium hydroxide for 24 hours.

Example 158 A reaction mixture was prepared by admixing 350.

parts of Epon 864, 20 parts of the phenolaldehyde condensate of Example17, 381 parts of 4,4--bis(4-hydroxyphenyl) pentanoic acid, and 15 partssodium ethoxide catalyst. The mixture was spread in wet films of .002thickness. Hard, tack-free, infusible brittle films were obtained bycuring the wet films at 175 C. for one hour.

Example 159 A reaction mixture was prepared by adrnixing'35 parts ofEpon 864, 360 parts of the phenol-aldehyde condensate of Example 16, and9.5 parts 4,4-bis(4-hydroxyphenyl) pentanoic acid. The mixture wasspread in wet films of .002" thickness. Hard, tack-free, somewhatbrittle, infusible films were obtained by curing the Wet films at 175 C.for one hour.

Example 160 A reaction mixture was prepared by admixing 300 parts of thepolyepoxide of Example 9, parts of the aldehyde condensate of Example 17and 64 parts of 4,4-bis (4-hydroxyphenyl) pentanoic acid. The mixturewas spread in wet films of .002 thickness and the wet films were curedby heating at 175 C. for 30 minutes. The cured films were hard, flexibleand tack-free. They with stood boiling water for 4 /2 hours and 5%sodium hydroxide for 1 /2 hours without deterioration.

Example 161 A reaction mixture was prepared by admixing 150 parts of thepolyepoxide of Example 9, .60 parts of the aldehyde condensate ofExample 17 and 95 parts of 4,4-bis(4-hydroxyphenyl) pentanoic acid. Themixture was spread in Wet films of .002 thickness and cured by heatingat 175 IC. for 30 minutes. The cured films were hard, flexible andtack-free. They withstood boiling water for 4 /2 hours and 5% sodiumhydroxide for 1% hours without deterioration.

Example 162 A reaction mixture was prepared by admixing 350 parts ofEpon 864, .3600 parts of the condensate of Example 11, 95 parts4,4-.bis(4-hydroxyphenyl) pentanoic acid, and 10 parts sodium ethoxide.The mixture was spread in Wet films of .002" thickness and cured at 175C. for 30 minutes. The cured films were hard, tack-free, and withstoodboiling water for 51/2 hours and 5% aqueous NaOH for 10 /2 hours.

Example 165' A reaction mixture was prepared by admixing 350 parts ofEpon 864, 3600 parts of the condensate of Example 13, 95 parts 4,.4-bis(4-l1ydroxyphenyl) pentanoic acid, and 10 parts sodium ethox-ide. Themixture was spread in wet films of .002 thickness and cured by heatingfor 30 minutes at 175 C. The cured films were hard and tack-free. Theywithstood boiling Water for 4 /2 hours and 5% aqueous NaOH for 10 /2hours.

Example 164 A reaction mixture was prepared by admixing 3500 parts ofEpon 864, 100 parts of the condensate of Ex ample 15, 3800 parts4,4-'bis'(4-hydroxyphenyl) pentanoic acid, and 100 parts sodiumethoxide. The mixture was spread in wet films of 002 thickness. Hard,itack free .filrns were obtained by heating the wet films for one hour91,175 C.

The cured films Example A reaction mixture was prepared by admixing 30parts of the polyepoxide polyester of Example 5, 300 parts of thecondensate of Example 12, 9.5 parts 4,4-bis.(4-hydroxyphenyl) peritanoicacid, and 1 part sodium ethoxide. The mixture was spread in wet films of.002 thickness. Hard, tack-free films were obtained by heating the wetfilms for 30 minutes at C. a

. Example 166 A reaction mixture was prepared by admixing 273 parts ofthe polyepoxide polyester of Example 7, 10'parts of the condensate ofExample 11, 286 parts 4,4-bisf(4-hydroxyphenyl) pentanoic acid, and 15parts sodium ethoxide. The mixture was spread in wet films of .002"thickness to provide hard, tack-free films by curing the wet fihns for30 minutes at 175 C.

Example 167 A reaction mixture was prepared by admixing 300 parts of thepolyepoxide of Example 9, 10 parts of the aldehyde condensate of Example13, and 64 parts of 4,4bis(4-hydroxyphenyl) pentanoic acid. The mixturewas spread in wet films of .002" thickness and cured by heating for 30minutes at 175 C. The cured films were hard, flexible, and tack-free.They withstood boiling water for 1 /2 hours and 5% sodium hydroxide for1: of an hour Withoutdeterioration.

Example 169 A reaction mixture was prepared by admixing 1150.

parts of the polyepoxide of Example 9, 40 parts 'of the aldehydecondensate of Example 12, and parts of 4,4-bis(4-hydroxyphenyl)pentanoic acid. The mixture was spread in wet films of .002" thicknessand cured by heating for 30 minutes at 175 C. The cured films were hard,flexible, and tack-free. They withstood boiling water for 4 /2 hours and5% sodium hydroxide for 2 minutes without deterioration.

It should be appreciated that the invention is not to be construed to belimited by the illustrationexamples. It is possible to produce stillother embodiments without departing from the inventive concept hereindisclosed. This application is a continuation-in-part of the Greenleecopending applications S. N. 541,022, 557,835, and 562,663, filedOctober 17, 1955, January 9, 1956, and February .1, 1956, respectively,now abandoned.

It is claimed and desired to secure by Letters Patent:

1. A composition of matter comprising the condensation product obtainedby heating (A) an organic poly epoxide having an average of more thanone epoxide group per molecule wherein the epoxy oxygen atom is linkedto adjacent carbon atoms and (B) ,a 4,4-bis(hydroxyaryllpentanoic acidwherein the hydroxyaryl radical is a member of the group consisting ofunsubstituted hydroxyphenyl and ring substituted hydroxyphenyl whereinthe hydroxy group of said member is in a position other than one meta tothe point of attachment of said member to the pentanoic acid, anysubstituent on the hydroxyphenyl being a member selected from the groupconsisting of chloro, bromo, nitro and al-kyl groups of from 1-5 carbonatoms and wherein the reactive oxirane groups of (A) and the reactivehydrogens of (B) are present in an equivalent ratio of from 6:1 to 1:6.

2. The composition of claim 1 wherein the reactive oxirane groups of (A)and the reactive hydrogens of (B) are present in an equivalent ratio offrom about 2:1 to 1:2.

3. A composition of matter comprising the condensation product obtainedby heating (A) an organic polyepoxide having an average of more than oneepoxide oxirane groups of (A) and the reatcive hydrogens of group permolecule wherein the epoxy oxygen atom is linked to adjacent carbonatoms, (B) a 4,4-bis(hydroxy aryl)pentanoic acid wherein the hydroxyarylradical is a member of the group consisting of unsubstitutedhydroxyphenyl and ring substituted hydroxyphenyl wherein the hydroxygroup of said member is in a position other than one meta to the pointof attachment of said memher to the pentanoic acid, any substituent onthe hydroxyphenyl being a member selected from the group consisting ofchloro, bromo, nitro and alkyl groups of from 1-5 carbon atoms andwherein the reactive oxirane groups of (A) and the reactive hyd-rogensof (B) are present in an equivalent ratio of from 6:1 to 1:6, and (C)from about 10-35% 011 a combined weight basis of (A) and (B) of afusible condensate of a monoaldehyde with at least one organic ammoniaderivative selected from the group con- Sisting of urea, thiourea,melamine, toluene sulfonamide and alkyl substituted derivatives thereof.

4. A composition of matter comprising the condensation product obtainedby heating (A) an organic polyepoxide having an average of more than oneepoxide group per molecule wherein the epoxy oxygen atom is linked toadjacent carbon atoms, (B) a 4,4-bis(hydroxyaryl)pentanoic acid whereinthe hydroxyaryl radical is a member of the group consisting ofunsubstituted hydroxyphenyl and ring substituted hydroxyphenyl whereinthe hydroxy group of said member is in a position other than one meta tothe point of attachment of said member to the pentanoic acid, anysubstituent on the hydroxyphenyl being a member selected from the groupconsisting of chloro, bromo, nitro and alkyl groups of from 1-5 carbonatoms 22 and wherein the reactive oxirane groups of (A) and the reactivehydrogens of (B) are present in an equivalent ratio of from 6:1 to 1:6,and (C) from about 1035% on a combined Weight basis of (A) and (B) of afusible condensate of a monoaldehyde with a phenol.

5. The composition of claim 1 wherein the pentanoic acid is4,4-bis(4-hydroxyphenyl) pentanoic acid.

6. The composition of claim 1 wherein the hydroxyaryl radical of thepentanoic acid is alkyl substituted.

7. The composition of claim 1 wherein said polyepoxide (A) is a complexepoxide which is a polymeric polyhydric alcohol having alternatingaliphatic chains and aromatic nuclei united through ether oxygen andterminating in epoxy-substituted aliphatic chains.

8. The composition of matter of claim 1 wherein said polyepoxide (A) isan epoxidized polyester of tetrahydrophthalic acid and a glycol, whereinthe epoxy oxygen atoms are each linked to adjacent carbon atoms in thenucleus of said acid.

9. The composition of matter of claim 1 wherein said polyepoxide (A) isan epoxidized ester of an unsaturated natural fatty oil acid containingabout 15-22 carbon atoms, and having its reactive groups selected fromthe class consisting of oxirane and hydroxy.

10. The composition of matter of claim 1 wherein said polyepoxide (A) isan aliphatic polyepoxide selected from the group consisting ofbis(glycidyloxy) butene, triglycidyl glyceryl ether, diepoxy butane, anddiglycide ether.

OTHER REFERENCES Bader et a1.: J.A.C.S., v01. 76, pages 4465-4466(September 5, 1954). (Copy in Scientific Library.)

UNITED STATES PATENT OFFICE Certificate of Correction Patent No.2,907,730 October 6, 1959 Sylvan Owen Greenlee It is hereby certifiedthat error appears in the printed specification of the above numberedpatent requiring correction and that the said Letters Patent shouldreacl as corrected below.

Column 1, line 25, after groups strike out or; column 2, line 16, forfunction read -functional-; line 35, for cabon read carbon; line 53, forWitht read -with-; line 64, for impartred read -imparted; column 7,lines 14 to 17, in Equation V, for the glycerol formula reading CHzOHCHzOH CHOH read HOH HOH H2OH column 8, line 49, for RR' N+OH read +RR N'OH- column 9, line 19, Example 8, for strokes read stokes-; column 10,line 23, for derivatives read derivative; columns 15 and 16, in thetable, sixth column thereof, in the headin for Diphenolic acid readDiphenolic Ac1d; columns 17 and 18, in the table, sixt column thereof,for Diphenolic acid read Diphenolic Acid; column 21, line 7, strike outoxirane groups of (A) and the reatcive hydrogens of.

Signed and sealed this 17th day of May 1960.

Attest: KARL. H. AXLINE, ROBERT C. WATSON, Attestz'ng Ofiicer.flommz'ssz'oner of Patents.

1. A COMPOSITION OF MATTER COMPRISING THE CONDENSATION PRODUCT OBTAINEDBY HEATING (A) AN ORGANIC POLYEPOXIDE HAVING AN AVERAGE OF MORE THAN ONEEPOXIDE GROUP PER MOLECULE WHEREIN THE EPOXY OXYGEN ATOM IS LINKED TOADJACENT CARBON ATOMS AND (B) A 4,4-BIS(HYDROXYARYL) PENTANIOC ACIDWHEREIN THE HYDROXYARYL RADICAL IS A MEMBER OF THE GROUP CONSISTING OFUNSUBSTITUTED HYDROXYPHENYL AND RING SUBSTITUTED HYDROXYPHENYL WHEREINTHE HYDROXY GROUP OF SAID MEMBER IS IN A POSITION OTHER THAN ONE META TOTHE POINT OF ATTACHMENT OF SAID MEMBER TO THE PENTANIOC ACID, ANYSUBSTITUENTS ON THE HYDROXYPHENYL BEING A MEMBER SELECTED FROM THE GROUPCONSISTING OF CHLORO, BROMO, NITRO AND ALKYL GROUPS OF CROM 1-5 CARBONATOMS AND REACTIVE HYDROIGENS OF (B) ARE GROUPS OF (A) AND THE REACTIVEHYDROGENS OF (B) ARE PRESENT IN AN EQUIVALENT RATIO OF FROM 6:1 TO 1:6.